Electronic structure and phosphorus shielding: transition between PN double and triple bonding in iminophosphines ROPNMes*

Gudat, Dietrich; Niecke, Edgar; Großmann, G.; Krüger, Kerstin

doi:10.1002/(sici)1097-458x(199901)37:1<43::aid-mrc407>3.0.co;2-a

Cited by 4 publications

(1 citation statement)

References 21 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…X-P=E with X an electronegative ligand and E = CR' 2 , NR' and PR') -see Ref. 4 and references therein. Both our compounds have been structurally characterized by diffraction methods 5,6 .…”

Section: Introductionmentioning

confidence: 99%

Structural and electronic information on two solid iminophosphoranes, obtained from NMR

Cherryman¹,

Harris²,

Davidson³

et al. 1999

J. Braz. Chem. Soc.

View full text Add to dashboard Cite

Neste trabalho foram obtidos os espectros de RMN CPMAS de fósforo-31 e carbono-13 do imino(trifenil)fosforano e do brometo de amino(trifenil)fosfônio. A análise detalhada desses espectros forneceu informações sobre o tensor de blindagem de 31 P e o tensor de acoplamento quadrupolar de 14 N. O espectro estático de 31 P do brometo foi também analisado em termos dos tensores relevantes. Os cálculos ab initio no nível hf/6-31g* reproduzem bem os dados observados, com exceção dos deslocamentos isotrópicos, os quais requerem cálculos com bases maiores e/ou de um nível teórico superior. As orientações dos tensores na estrutura do brometo foram derivadas através dos cálculos. Phosphorus-31 and carbon-13 CPMAS NMR spectra have been obtained for imino(triphenyl)phosphorane and amino(triphenyl)phosphonium bromide. Detailed analysis yields information about the 31 P shielding tensor and the 14 N quadrupole coupling tensor. The static 31 P spectrum of the bromide was also analysed in terms of the relevant tensors. Ab initio calculations at the hf/6-31g* level reproduce the observed data well, except for the isotropic shifts, which require a larger basis set and/or higher level of theory. The orientations of the tensors in the molecular frame are derived for the bromide from the calculations.

show abstract

Section: Introductionmentioning

confidence: 99%